CN103706388B - Composite of N doping porous carbon enveloped carbon nanometer tube and its preparation method and application - Google Patents
Composite of N doping porous carbon enveloped carbon nanometer tube and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to composite of N doping porous carbon enveloped carbon nanometer tube and its preparation method and application.The present invention by carbon nanotube dispersed in water, add carbon source and obtain reaction system, then carry out hydro-thermal reaction, have the CNT of carbonaceous layer and nitrogenous source at high temperature to heat-treat the Surface coating obtained, obtain the composite of N doping porous carbon enveloped carbon nanometer tube.Preparation method of the present invention mainly utilizes carbon source, under hydrothermal reaction condition, polymerization obtains carbonaceous layer, and be coated on the outer surface of CNT, then carbonaceous layer under high-temperature process carbonization decompose produce loose structure, the nitrogenous source simultaneously gasified by duct diffuse to carry out in carbonaceous layer in-situ doped.The cathodic oxygen reduction catalyst that composite of the present invention can be used as fuel cell uses, and catalytic performance is excellent, has higher oxygen reduction activity compared with other N doping material of bibliographical information.Preparation method's technique of the present invention is simple, economical, operation is convenient, be easy to large-scale production.
Description
Technical field
The present invention relates to composite of N doping porous carbon enveloped carbon nanometer tube and preparation method thereof, and this composite is as the application of oxygen reduction catalyst.
Background technology
Fuel cell is a kind of cleanliness without any pollution and the TRT having very high energies conversion efficiency, in the great energy problem of solution, account for very important status.But the Cathodic oxygen reduction dynamics of its key is slow, needs rare noble metal as catalyst, this just serious extensive use hindering fuel cell.Many people start to utilize noble metal and other special construction such as transition metal component alloy or nucleocapsid, improve the utilization rate of noble metal and reduce its carrying capacity, but this can not break away from the limitation of noble metal itself all the time.Therefore, the concern that the non-precious metal catalyst with high oxygen reduction catalytic activity is more and more subject to people is developed.
As far back as the seventies in last century six, the material with carbon element of doping is just considered to good oxygen reduction non-noble metal catalyst.In recent years, some highly active doping carbon materials were in the news.And due to its cheapness and good anti methanol toxication performance, doping carbon material is considered to likely substitute one of material of noble metal catalyst in future.In numerous hetero atom, the doping of nitrogen-atoms is studied by people the earliest.At present, prepare nitrogen-doped carbon material and mainly contain three kinds of methods: one is in-situ doped method, namely adulterate while growth carbon skeleton, such as chemical vapour deposition (CVD), this preparation method often can adulterate the hetero atom of high-load, but the preparation condition of the equipment of its costliness and sensitivity is unfavorable for the large-scale production of catalyst.Two is post processing doping methods, generally that the graphitized carbon material of conduction is at high temperature processed adulterate with containing heteroatomic compound, because carbonization structure brings resistance to doping, therefore heteroatomic content is usually lower, can not obtain desirable catalytic activity.For above-mentioned two kinds of method Problems existing, there has been proposed the third doping method, by low degree of graphitization or do not have the nitrogenous material with carbon element of carbonization structure directly to carry out high-temperature process, solve the problem that content of heteroatoms is lower, and then with some conductive carbon skeleton compounds, improve the mobility of electronics in catalytic process.CNT has been widely studied and actual use as the carrier of catalyst, and its specific area and good electric conductivity effectively can improve the catalyst performance of compound.But, how by CNT and the suitable compound of nitrogenous material with carbon element, improve heteroatomic utilization rate and still there is very large challenge at present.
Therefore, develop a kind of simple, economical, green, hetero atom can be made full use of, be suitable for the technology tool preparing CNT and nitrogenous material with carbon element compound of large-scale production and be of great significance.
Summary of the invention
An object of the present invention is to provide the composite of N doping porous carbon enveloped carbon nanometer tube.
Two of object of the present invention is to provide a kind of preparation method of composite of N doping porous carbon enveloped carbon nanometer tube.
Three of object of the present invention is to provide the application of composite as oxygen reduction catalyst of N doping porous carbon enveloped carbon nanometer tube.
The composite of N doping porous carbon enveloped carbon nanometer tube of the present invention is by the CNT as inner layer conductive network and form at the nitrogen-doped porous carbon material shell of described CNT outer cladding.
The length of described CNT can be 1 ~ 30 micron, is preferably 5 ~ 15 microns; Diameter can be 10 nanometer ~ 100 nanometers, is preferably 40 ~ 60 nanometers.
The thickness of described nitrogen-doped porous carbon material shell can be 10 nanometer ~ 100 nanometers, is preferably 20 nanometer ~ 50 nanometers.
Described N doping porous carbon, the content of its nitrogen-atoms is 3 ~ 15%, is preferably 5 ~ 10%.
The pore size in the hole in described porous carbon is 1 nanometer ~ 20 nanometer, is preferably 2 nanometer ~ 5 nanometers.
The specific area of described composite is 100 ~ 500m
2/ g, is preferably 200 ~ 500m
2/ g.
The preparation method of the composite of N doping porous carbon enveloped carbon nanometer tube of the present invention is:
By carbon nanotube dispersed in water, add carbon source and obtain reaction system, then carry out hydro-thermal reaction, obtain the CNT that Surface coating has carbonaceous layer; There are the CNT of carbonaceous layer and nitrogenous source at high temperature to heat-treat the Surface coating obtained, obtain the composite of N doping porous carbon enveloped carbon nanometer tube.
The temperature of described hydro-thermal reaction is 120 DEG C ~ 190 DEG C, is preferably 180 DEG C; Reaction time is 6 ~ 20 hours, is preferably 10 ~ 15 hours.
Described heat treated temperature is 600 DEG C ~ 1000 DEG C, is preferably 800 DEG C ~ 1000 DEG C, most preferably is 900 DEG C.
In described reaction system, the mass ratio that feeds intake of CNT and carbon source is 1:20 ~ 1:60, is preferably 1:40.
Described Surface coating has the mass ratio that feeds intake of the CNT of carbonaceous layer and nitrogenous source to be 1:5 ~ 1:20, is preferably 1:10.
Described carbon source is selected from one or more in glucose, dopamine, polyaniline, is preferably glucose.
Described nitrogenous source is selected from one or more in melamine, nitrile ammonia, two nitrile ammonia, urea, is preferably melamine.
Preparation method of the present invention is simple, economy, products obtained therefrom nitrogen content are high, the composite of the N doping porous carbon enveloped carbon nanometer tube that can be mass-produced, and the cathodic oxygen reduction catalyst that this composite can be used as fuel cell uses.
Preparation method of the present invention mainly utilizes carbon source, under hydrothermal reaction condition, polymerization obtains carbonaceous layer, and be coated on the outer surface of CNT, then carbonaceous layer under high-temperature process carbonization decompose produce loose structure, the nitrogenous source simultaneously gasified by duct diffuse to carry out in carbonaceous layer in-situ doped.
The present invention, compared with other prior art, has following characteristics:
1, adopt hydro-thermal method at the coated carbonaceous layer of the outer surface of CNT in the present invention, with other method as solution mutually in concentrated sulfuric acid carbonized sucrose compare, hydro-thermal method is simple, and covered effect is better, and thickness is easy to control, and is suitable for large-scale production.
2, hydro-thermal method is adopted to prepare the carbonaceous layer of enveloped carbon nanometer tube in the present invention, again through high-temperature process doping nitrogen, compared to other, high-temperature process of graphitized carbon material is adulterated, the carbonization of carbonaceous layer is decomposed nitrogenous source that the loose structure produced is conducive to gasifying and is carried out original position to carbonaceous layer and efficiently adulterate, and described loose structure can accelerate the mass transport process of electrochemical reaction.
3, adopt cheap melamine, cyanamide etc. be nitrogenous source in the present invention, with other nitrogenous source as compared with ammonia, hydrogen cyanide, melamine doped process is relatively safe, and inventory is easy to control.
4, the doping method adopted in the present invention is adulterated when carbon atom trends towards graphitization, the in-situ doped method of this kind and other method are as in-situ doped and post processing doping, higher nitrogen atom content can either be obtained, catalyst can be made again to keep having good electric conductivity.
5, the catalytic performance of composite prepared of the present invention is excellent, has higher oxygen reduction activity compared with other N doping material of bibliographical information.
6, method technique of the present invention is simple, economical, operation is convenient, be easy to large-scale production, has huge potential using value at many industrial catalysts or other scientific domain.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of the composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube.
Fig. 2 is specific area test curve (a) and pore-size distribution test curve (b) of the composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube.
Fig. 3 is that the photoelectron spectroscopy of the composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube sweeps spectrogram (a) and N1s swarming spectrogram (b) entirely.
Fig. 4 is the hydrogen reduction empirical curve of the composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use.
Fig. 5 is methanol tolerance test experiments curve (a) of composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube and methanol tolerance test experiments curve (b) of the carbon supported platinum catalyst of commercial use.
Fig. 6 is the stability test empirical curve of the composite of embodiment 1 gained N doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Embodiment 1
By 20mg CNT (diameter 40 nanometer to 60 nanometer, length 5 microns to 15 microns) ultrasonic disperse after 1 hour in 10mL water, add 800mg glucose, be transferred to until completely dissolved in autoclave that 25mL take polytetrafluoroethylene (PTFE) as liner, then at temperature is 180 DEG C, carry out hydro-thermal reaction 15 hours, through water, ethanol washing for several times, suction filtration, obtain solid, spend the night 60 DEG C of oven dry, obtaining Surface coating has thickness to be about the CNT of 25 ~ 35 nanometer carbonaceous layers; The CNT of carbonaceous layer and melamine is had by the Surface coating obtained to be after the ratio of 1:10 mixes with mass ratio; be transferred in porcelain boat; and insert in the quartz ampoule of tube furnace; with argon gas except air half an hour; be warming up to 900 DEG C again; heat-treat two hours under argon shield after, obtain the composite of N doping porous carbon enveloped carbon nanometer tube.
The transmission electron microscope photo of the composite of gained N doping porous carbon enveloped carbon nanometer tube as shown in Figure 1, composite described is as seen from the figure by the CNT as inner layer conductive network and form at the nitrogen-doped porous carbon material shell of described CNT outer cladding, and the thickness of described shell is about 25 ~ 35 nanometers.
As shown in Figure 2, adsorption-desorption curve is shown in (a) figure, and pore-size distribution test curve is shown in (b) figure in the specific area test of the composite of gained N doping porous carbon enveloped carbon nanometer tube.As seen from the figure, described composite has micropore and meso-hole structure, and its specific area is 413m
2/ g.From pore size distribution curve, the most of scope in 1 ~ 4 nanometer in aperture in the hole in the N doping porous carbon in described composite.
The photoelectron spectroscopy of the composite of gained N doping porous carbon enveloped carbon nanometer tube entirely sweeps spectrogram and N1s swarming spectrogram is shown in Fig. 3 respectively, and wherein, photoelectron spectroscopy is entirely swept spectrogram and seen (a) figure, and N1s swarming spectrogram is shown in (b) figure.As seen from the figure, nitrogen element is successfully doped in carbonaceous layer, and the content of nitrogen-atoms is 6.93%, and wherein main component is the pyridine type nitrogen and quaternary nitrogen that oxygen reduction catalytic activity is high.
Therefore from above-mentioned data, described composite is by the CNT as inner layer conductive network and form at the nitrogen-doped porous carbon material shell of described CNT outer cladding, and the cathodic oxygen reduction catalyst that described composite can be used as fuel cell uses; Wherein, at 900 DEG C, heat treatment is after two hours, and the thickness of the nitrogen-doped porous carbon material shell obtained is about 25 ~ 35 nanometers, and the specific area of described composite is 413m
2/ g, the content of nitrogen-atoms in described composite is 6.93%.
The hydrogen reduction empirical curve of the composite of gained N doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use as shown in Figure 4.Concrete test method is: hydrogen reduction empirical curve rotating disk electrode (r.d.e) is measured in the potassium hydroxide solution of 0.1 mol/L, and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and curved scanning speed is 5 millivolts/second.
Contrasting with the carbon supported platinum catalyst of commercial use is buy to believe that the platinum weight percentage of ten thousand rich (Johnson-Matthey) (Shanghai) catalyst Co., Ltd is the business carbon supported platinum catalyst of 20% from the village.
Relatively two curves, can find out, the half wave potential of composite performance in hydrogen reduction experiment of the above-mentioned N doping porous carbon enveloped carbon nanometer tube prepared is-0.184V relative to the current potential of silver/silver chloride reference electrode (electrolyte is the aqueous solution of potassium nitrate mass fraction 10%), than the half wave potential-0.142V only negative 42mV of business carbon supported platinum catalyst, therefore show good hydrogen reduction electro catalytic activity.
The methanol tolerance test experiments curve of the composite of gained N doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use is shown in Fig. 5, wherein: the methanol tolerance test experiments curve of described composite is shown in (a) figure, the methanol tolerance test experiments curve of the carbon supported platinum catalyst of commercial use is shown in (b) figure.Concrete test method is: hydrogen reduction empirical curve rotating disk electrode (r.d.e) is measured in the potassium hydroxide solution of 0.1 mol/L containing 0.5 mol/L methyl alcohol, and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and curved scanning speed is 5 millivolts/second.
Curve relatively in two figure, can find out that the composite relative commercial carbon supported platinum catalyst of the N doping porous carbon enveloped carbon nanometer tube that the present embodiment prepares has fabulous anti methanol toxication performance.
The stability test empirical curve of the composite of gained N doping porous carbon enveloped carbon nanometer tube and the carbon supported platinum catalyst of commercial use is shown in Fig. 6.Concrete test method is: hydrogen reduction empirical curve rotating disk electrode (r.d.e) is measured in the potassium hydroxide solution of saturated 0.1 mol/L of oxygen, and the rotating speed of rotating disk electrode (r.d.e) is 1600 revs/min, and constant potential is-0.2V, and test time is 20000 seconds.
Relatively two curves, can find out that the composite relative commercial carbon supported platinum catalyst of the N doping porous carbon enveloped carbon nanometer tube that the present embodiment prepares has better stability.
Embodiment 2
Substantially prepare the composite of N doping porous carbon enveloped carbon nanometer tube according to the method identical with embodiment 1, difference is changed to 800 DEG C by adopt during heat treatment 900 DEG C, and the specific area of the composite obtained is 101m
2/ g, wherein the thickness of the coated shell of N doping porous carbon is about 30 ~ 40 nanometers, and the content of nitrogen-atoms is 15.76%.
Embodiment 3
Substantially prepare the composite of N doping porous carbon enveloped carbon nanometer tube according to the method identical with embodiment 1, difference is changed to 1000 DEG C by adopt during heat treatment 900 DEG C, and the specific area of the composite obtained is 479m
2/ g, wherein the thickness of the coated shell of N doping porous carbon is about 10 ~ 20 nanometers, and the content of nitrogen-atoms is 3.54%.
Embodiment 4
Substantially the composite of N doping porous carbon enveloped carbon nanometer tube is prepared according to the method identical with embodiment 1, difference is that 1:60 feeds intake by CNT and glucose according to mass ratio, and in the composite obtained, the thickness of the coated shell of N doping porous carbon is about 50 ~ 60 nanometers.
Embodiment 5
Substantially the composite of N doping porous carbon enveloped carbon nanometer tube is prepared according to the method identical with embodiment 1, difference adopts length to be 1 ~ 5 micron, diameter is the CNT of 10 ~ 30 nanometers is raw material, be that 1:20 feeds intake by CNT and glucose according to mass ratio, the temperature of hydro-thermal reaction is changed to 120 DEG C, the time of hydro-thermal reaction is changed to 6 hours, and in the composite obtained, the thickness of the coated shell of N doping porous carbon is about 10 ~ 20 nanometers.
Embodiment 6
Substantially the composite of N doping porous carbon enveloped carbon nanometer tube is prepared according to the method identical with embodiment 1, difference adopts length to be 20 ~ 30 microns long, diameter is the CNT of 80 ~ 100 nanometers is raw material, be that 1:60 feeds intake by CNT and glucose according to mass ratio, the time of hydro-thermal reaction is changed to 20 hours, the temperature of hydro-thermal reaction is changed to 190 DEG C, be changed to 600 DEG C by adopt during heat treatment 900 DEG C, in the composite obtained, the thickness of the coated shell of N doping porous carbon is about 90 ~ 100 nanometers.
Embodiment 7
Substantially the composite of N doping porous carbon enveloped carbon nanometer tube is prepared according to the method identical with embodiment 1, difference adopts dopamine to replace glucose as carbon source, and being had by Surface coating the CNT of carbonaceous layer and melamine to be that 1:5 feeds intake according to mass ratio, in the composite obtained, the content of nitrogen-atoms is 4.69%.
Embodiment 8
Substantially the composite of N doping porous carbon enveloped carbon nanometer tube is prepared according to the method identical with embodiment 1, difference adopts nitrile ammonia to replace melamine as nitrogenous source, and being had by Surface coating the CNT of carbonaceous layer and nitrile ammonia to be that 1:20 feeds intake according to mass ratio, in the composite obtained, the content of nitrogen-atoms is 8.37%.
It should be noted that, above-described embodiment is only used to technical characteristic of the present invention is described, is not used to limit the claimed scope of the present invention.The carbon source related in such as embodiment, nitrogenous source, also can use other reactant, but this type of in-situ doped method still belongs to the claimed category of the present invention.
Claims (8)
1. a composite for N doping porous carbon enveloped carbon nanometer tube, is characterized in that: described composite is by the CNT as inner layer conductive network and form at the nitrogen-doped porous carbon material shell of described CNT outer cladding; Described N doping porous carbon, the content of its nitrogen-atoms is 3 ~ 15%;
The composite of described N doping porous carbon enveloped carbon nanometer tube is obtained by following preparation method: by carbon nanotube dispersed in water, add carbon source and obtain reaction system, then carry out hydro-thermal reaction, obtains the CNT that Surface coating has carbonaceous layer; There are the CNT of carbonaceous layer and nitrogenous source to heat-treat the Surface coating obtained, obtain the composite of N doping porous carbon enveloped carbon nanometer tube;
Described carbon source is selected from glucose;
Described nitrogenous source is selected from one or more in melamine, nitrile ammonia, two nitrile ammonia, urea.
2. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the length of described CNT is 1 ~ 30 micron, and diameter is 10 nanometer ~ 100 nanometers.
3. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the thickness of described nitrogen-doped porous carbon material shell is 10 nanometer ~ 100 nanometers.
4. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the specific area of described composite is 100 ~ 500m
2/ g.
5. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: the temperature of described hydro-thermal reaction is 120 DEG C ~ 190 DEG C, and the reaction time is 6 ~ 20 hours;
Described heat treated temperature is 600 DEG C ~ 1000 DEG C.
6. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: in described reaction system, and the mass ratio that feeds intake of CNT and carbon source is 1:20 ~ 1:60.
7. the composite of N doping porous carbon enveloped carbon nanometer tube according to claim 1, is characterized in that: described Surface coating has the mass ratio that feeds intake of the CNT of carbonaceous layer and nitrogenous source to be 1:5 ~ 1:20.
8. an application for the composite of the N doping porous carbon enveloped carbon nanometer tube described in claim 1 ~ 7 any one, is characterized in that: the composite of described N doping porous carbon enveloped carbon nanometer tube uses as the cathodic oxygen reduction catalyst of fuel cell.
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